CN102633687B - The preparation method of a kind of para-orientation alkylbenzene sulfonyl chloride and technique - Google Patents
The preparation method of a kind of para-orientation alkylbenzene sulfonyl chloride and technique Download PDFInfo
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Abstract
The preparation method of a kind of para-orientation alkylbenzene sulfonyl chloride and technique, step is as follows: 1) add alkylbenzene and inorganic salt catalyst in reactor, in 0 DEG C of disposable slow addition chlorosulfonic acid of-45 DEG C of temperature under stirring, insulation reaction 0.1-10 hour, obtain sulfonation material; 2) adopt frozen water deposition method to separate and purify para-orientation alkylbenzene sulfonyl chloride. Beneficial effects of the present invention: adopt the inorganic salts such as sodium sulfate can effectively suppress the carrying out of the side reaction in sulfonating reaction and chlorosulfonation process as catalyst, decrease the generation of by-product, thus improve the yield of alkylbenzene sulfonyl chloride, yield is up to 90-99%; In addition the technique taking low temperature sulfonation, chloride, simplifies operating process, is effectively shortened the production cycle, solves the problems such as inorganic acid chloride cost in existing method and technique is high, toxicity is relatively big, three-protection design difficulty, organic solvent recovery.
Description
Technical field
The preparation method of the preparation method that the present invention relates to para-orientation alkylbenzene sulfonyl chloride, particularly a kind of para-orientation alkylbenzene sulfonyl chloride and technique.
Background technology
Alkylbenzene sulfonyl chloride is widely used in the important intermediate of medicine, dyestuff, pigment, auxiliary agent etc. The common method of current industrial production alkylbenzene sulfonyl chloride, is react alkylbenzene and excessive chlorosulfonic acid to prepare. In order to improve the yield of sulfonic acid chloride product, generally requiring and promote to react completely with chlorosulfonic acid excessive in a large number, even so, the yield of usual sulfonic acid chloride product also only has about 80%, and product yield is relatively low, and spent acid amount is big, and environmental pollution is comparatively serious. For this, German patent DE 1172258, DE1112978, US Patent No. 3686300, the clear 56-46860 of Japan Patent JP, Chinese patent CN1824649, CN1405151, CN1049213C, CN1436773A, CN1569825A etc., by adding some auxiliary agent, as inorganic ammonium salt, alkali metal, alkaline-earth metal etc. reduce the generation amount of isomer in sulfonation process, to improve the yield of sulfonic acid chloride product, or by adding some inorganic acid chloride, if phosphorous oxychloride, thionyl chloride, phosphorus oxychloride etc. are to improve chlorosulfonation yield.
Our research finds, reaction for alkylbenzene Yu chlorosulfonic acid, although the addition of above-claimed cpd can reduce the generation amount of isomer to a certain extent, improve chlorosulfonation effect, but can not effectively suppress and eliminate the generation of sulfoxide compound and isomers, and owing to relatively costly, the toxicity of above-mentioned inorganic acid chloride is relatively big, cause production relatively costly, the problems such as three-protection design difficulty, are difficult to popularization and application in actual production.
Summary of the invention
It is an object of the invention to for above-mentioned existing problems, preparation method and the technique of a kind of para-orientation alkylbenzene sulfonyl chloride are provided, the method utilizes the space steric effect of alkyl in alkylbenzene molecule, low temperature process is adopted to carry out sulfonation and acyl chloride reaction, utilize inorganic salt can suppress the character that sulfoxide compound generates, adopt inorganic salt as catalyst, utilize alkylbenzene sulfonyl chloride under low temperature to be insoluble in water and stability is higher, adopt frozen water dilution deposition method separation product, prepare high yield, highly purified para-orientation alkylbenzene sulfonyl chloride.
Technical scheme:
The preparation method of a kind of para-orientation alkylbenzene sulfonyl chloride and technique, step is as follows:
1) reactor adds alkylbenzene and inorganic salt catalyst, in 0 DEG C of disposable slow addition chlorosulfonic acid of-45 DEG C of temperature under stirring, insulation reaction 0.1-10 hour, react complete and obtain sulfonation material;
2) adopting frozen water deposition method to separate and purify para-orientation alkylbenzene sulfonyl chloride, method is under agitation to be added slowly in frozen water by above-mentioned sulfonation material, then stratification, collects lower floor's Organic substance, prepares product alkylbenzene sulfonyl chloride.
Described alkylbenzene is toluene, ethylbenzene, n-propylbenzene, cumene, n-butylbenzene, isobutyl-benzene or tert-butyl benzene.
Described inorganic salt is the mixture of one or more arbitrary proportions in sodium sulfate, potassium sulfate, magnesium sulfate, calcium sulfate, iron sulfate, ammonium sulfate, sodium bisulfate, potassium acid sulfate, Magnesium hydrogen sulfate, calcium bisulfate, ammonium hydrogen sulfate, sodium chloride, potassium chloride, calcium chloride, magnesium chloride, iron chloride, ammonium chloride, sodium bromide, potassium bromide, magnesium bromide, calcium bromide and ammonium bromide, and the mol ratio of inorganic salt and alkylbenzene is 0.001-0.50: 1.
The purity of described chlorosulfonic acid is >=92%, and the mol ratio that the consumption of chlorosulfonic acid is chlorosulfonic acid and alkylbenzene is 2.5-6.0: 1.
In described frozen water deposition method 0.5-10.0 times that consumption is sulfonation quality of material of frozen water.
Beneficial effects of the present invention: adopt the inorganic salts such as sodium sulfate can effectively suppress the carrying out of the side reaction in sulfonating reaction and acyl chloride reaction process as catalyst, decrease the generation of by-product, thus improve the yield of para-orientation alkylbenzene sulfonyl chloride, yield is up to 90-99%; In addition the technique taking low temperature sulfonation, chloride, simplifies operating process, is effectively shortened the production cycle, solves the problems such as inorganic acid chloride cost in existing method and technique is high, toxicity is relatively big, three-protection design difficulty, organic solvent recovery.
Detailed description of the invention
Below in conjunction with specific embodiment, the invention will be further described, but embodiment is not intended to protection scope of the present invention.
Embodiment 1:
The preparation method of a kind of para-orientation alkylbenzene sulfonyl chloride and technique, step is as follows:
1) in 1000mL four-hole bottle, add toluene 55.2g, stirring is lower adds sodium sulfate 3.6g, ice bath is cooled to less than 10 DEG C, controls reaction temperature and is 10-20 DEG C, controls 2.0-2.5 hour, chlorosulfonic acid 216.2g is dripped slowly from Dropping funnel, dropping is finished, and in 15-20 DEG C of insulation reaction 2h, obtains sulfonation material;
2), in 1000mL beaker, add mixture of ice and water 150g, start stirring, being added slowly in frozen water by above-mentioned sulfonation material, in less than 15 DEG C maintenance effects 15 minutes, sucking filtration obtained white solid, 4-toluene sulfonyl chloride 103.8g, yield 90.8%, m.p.64-67 DEG C.
Embodiment 2:
The preparation method of a kind of para-orientation alkylbenzene sulfonyl chloride and technique, step is as follows:
1) in 1000mL four-hole bottle, add toluene 55.2g, stirring is lower adds sodium sulfate 7.2g, ice bath is cooled to less than 10 DEG C, controls reaction temperature and is 15-20 DEG C, controls 1.5-2.0 hour, chlorosulfonic acid 216.2g is dripped slowly from Dropping funnel, dropping is finished, and in 15-20 DEG C of insulation reaction 2.5h, obtains sulfonation material;
2), in 1000mL beaker, add mixture of ice and water 150g, start stirring, being added slowly in frozen water by above-mentioned sulfonation material, in less than 15 DEG C maintenance effects 25 minutes, sucking filtration obtained white solid 4-toluene sulfonyl chloride 104.5g, yield 91.4%, m.p.64-67 DEG C.
Embodiment 3:
The preparation method of a kind of para-orientation alkylbenzene sulfonyl chloride and technique, step is as follows:
1) in 1000mL four-hole bottle, add ethylbenzene 63.6g, stirring is lower adds sodium sulfate 3.6g, ice bath is cooled to less than 10 DEG C, controls reaction temperature and is 10-20 DEG C, controls 1.5-2.0 hour, chlorosulfonic acid 216.2g is dripped slowly from Dropping funnel, dropping is finished, and in 15-20 DEG C of insulation reaction 2h, obtains sulfonation material;
2) in 1000mL beaker, add mixture of ice and water 150g, start stirring, above-mentioned sulfonation material is added in frozen water slowly, in less than 15 DEG C maintenance effects 15 minutes, material is placed in separatory funnel and stands 30 minutes, separate lower organic layer and obtain 4-ethylo benzene sulfonic acid chloride 114.7g, yield 93.5%.
Embodiment 4:
The preparation method of a kind of para-orientation alkylbenzene sulfonyl chloride and technique, step is as follows:
1) in 1000mL four-hole bottle, add ethylbenzene 63.6g, stirring is lower adds potassium sulfate 6.6g, ice bath is cooled to less than 10 DEG C, controls reaction temperature and is 15-20 DEG C, controls 2.5-3.0 hour, from the disposable slow dropping chlorosulfonic acid 216.2g of Dropping funnel, dropping is finished, and in 15-20 DEG C of insulation reaction 2h, obtains sulfonation material;
2) in 1000mL beaker, add mixture of ice and water 150g, start stirring, above-mentioned sulfonation material is added in frozen water slowly, in less than 15 DEG C maintenance effects 25 minutes, material is placed in separatory funnel and stands 30 minutes, separate lower organic layer and obtain 4-ethylo benzene sulfonic acid chloride 115.6g, yield 94.2%.
Embodiment 5:
The preparation method of a kind of para-orientation alkylbenzene sulfonyl chloride and technique, step is as follows:
1) in 1000mL four-hole bottle, add isopropylbenzene 72.0g, stirring is lower adds sodium sulfate 3.6g, ice bath is cooled to less than 10 DEG C, controls reaction temperature and is 10-20 DEG C, controls 2.5-3.0 hour, from the disposable slow dropping chlorosulfonic acid 216.2g of Dropping funnel, dropping is finished, and in 15-20 DEG C of insulation reaction 2h, obtains sulfonation material;
2) in 1000mL beaker, add mixture of ice and water 150g, start stirring, above-mentioned sulfonation material is added in frozen water slowly, in less than 15 DEG C maintenance effects 15 minutes, material is placed in separatory funnel and stands 30 minutes, separate lower organic layer, obtain 4-Isopropylbenzenesulfonyl chloride 124.8g, yield 95.2%.
Embodiment 6:
The preparation method of a kind of para-orientation alkylbenzene sulfonyl chloride and technique, step is as follows:
1) in 1000mL four-hole bottle, add isopropylbenzene 72.0g, stirring is lower adds sodium sulfate 7.2g, ice bath is cooled to less than 10 DEG C, controls reaction temperature and is 15-20 DEG C, controls 1.5-2.0 hour, from the disposable slow dropping chlorosulfonic acid 216.2g of Dropping funnel, dropping is finished, and in 15-20 DEG C of insulation reaction 2h, obtains sulfonation material;
2) in 1000mL beaker, add mixture of ice and water 150g, start stirring, above-mentioned sulfonation material is added in frozen water slowly, in less than 15 DEG C maintenance effects 25 minutes, material is placed in separatory funnel and stands 30 minutes, separate lower organic layer, obtain 4-Isopropylbenzenesulfonyl chloride 125.8g, yield 96.0%.
Embodiment 7:
The preparation method of a kind of para-orientation alkylbenzene sulfonyl chloride and technique, step is as follows:
1) in 1000mL four-hole bottle, add tert-butyl benzene 80.4g, stirring is lower adds sodium sulfate 3.6g, ice bath is cooled to less than 10 DEG C, controls reaction temperature and is 10-20 DEG C, controls 1.5-2.0 hour, from the disposable slow dropping chlorosulfonic acid 216.2g of Dropping funnel, dropping is finished, and in 15-20 DEG C of insulation reaction 2h, obtains sulfonation material;
2), in 1000mL beaker, add mixture of ice and water 150g, start stirring, being added slowly in frozen water by above-mentioned sulfonation material, in less than 15 DEG C maintenance effects 15 minutes, sucking filtration obtained white solid 4-t-butylbenzenesulfonyl chloride 134.4g, yield 96.3%, m.p.76-78 DEG C.
Embodiment 8:
The preparation method of a kind of para-orientation alkylbenzene sulfonyl chloride and technique, step is as follows:
1) in 1000mL four-hole bottle, add tert-butyl benzene 80.4g, stirring is lower adds potassium sulfate 7.6g, ice bath is cooled to less than 10 DEG C, controls reaction temperature and is 15-20 DEG C, controls 2.0-2.5 hour, from the disposable slow dropping chlorosulfonic acid 216.2g of Dropping funnel, dropping is finished, and in 15-20 DEG C of insulation reaction 1.5h, obtains sulfonation material;
2), in 1000mL beaker, add mixture of ice and water 150g, start stirring, being added slowly in frozen water by above-mentioned sulfonation material, in less than 15 DEG C maintenance effects 25 minutes, sucking filtration obtained white solid 4-t-butylbenzenesulfonyl chloride 135.3g, yield 97.0%, m.p.76-78 DEG C.
Claims (1)
1. the preparation method of a para-orientation alkylbenzene sulfonyl chloride, it is characterised in that step is as follows:
1) reactor adds alkylbenzene and inorganic salt catalyst, in 0 DEG C of disposable slow addition chlorosulfonic acid of-45 DEG C of temperature under stirring, insulation reaction 0.1-10 hour, react complete and obtain sulfonation material;
2) adopting frozen water deposition method to separate and purify para-orientation alkylbenzene sulfonyl chloride, method is under agitation to be added slowly in frozen water by above-mentioned sulfonation material, then stratification, collects lower floor's Organic substance, prepares product alkylbenzene sulfonyl chloride;
Described alkylbenzene is toluene, ethylbenzene, n-propylbenzene, cumene, n-butylbenzene, isobutyl-benzene or tert-butyl benzene;
Described inorganic salt is the mixture of one or more arbitrary proportions in sodium sulfate, potassium sulfate, magnesium sulfate, calcium sulfate, iron sulfate, ammonium sulfate, sodium bisulfate, potassium acid sulfate, Magnesium hydrogen sulfate, calcium bisulfate, ammonium hydrogen sulfate, sodium chloride, potassium chloride, calcium chloride, magnesium chloride, iron chloride, ammonium chloride, sodium bromide, potassium bromide, magnesium bromide, calcium bromide and ammonium bromide, and the mol ratio of inorganic salt and alkylbenzene is 0.001-0.50:1;
The purity of described chlorosulfonic acid is >=92%, and the mol ratio that the consumption of chlorosulfonic acid is chlorosulfonic acid and alkylbenzene is 2.5-6.0:1;
In described frozen water deposition method 0.5-10.0 times that consumption is sulfonation quality of material of frozen water.
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| CN105037224A (en) * | 2015-05-27 | 2015-11-11 | 南通沃兰化工有限公司 | Method for reducing loss and improving yield during acyl chloride hydrolysis process |
| CN105503671A (en) * | 2015-12-22 | 2016-04-20 | 嘉兴学院 | Preparation method of p-toluene sulfonyl chloride |
| CN109456232A (en) * | 2018-12-17 | 2019-03-12 | 苏州华道生物药业股份有限公司 | A kind of preparation process of pair of ethyl beneznesulfonamide |
| CN109651206A (en) * | 2019-01-14 | 2019-04-19 | 杭州海虹精细化工有限公司 | A method of chlorosulfonation is carried out using sulfur trioxide |
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| DE1172258B (en) * | 1963-02-14 | 1964-06-18 | Basf Ag | Process for the continuous production of toluenesulfonic acid chlorides |
| US3686300A (en) * | 1969-03-14 | 1972-08-22 | Joachim Oten | Process for the preparation of p-toluenesulfochloride |
| CN1163264A (en) * | 1997-03-10 | 1997-10-29 | 刘国梁 | Process for producing p-toluenesulfonyl chloride |
| CN1405151A (en) * | 2002-11-04 | 2003-03-26 | 武汉大学 | Method for preparing sulfonyl chloro aromatics |
| CN1436773A (en) * | 2003-01-20 | 2003-08-20 | 浙江大学 | Synthesis process of tolylsulfonyl chloride |
| CN1569825A (en) * | 2003-07-17 | 2005-01-26 | 东港工贸集团有限公司 | Process for preparing arylsulfuryl chloride derivatives |
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| US5877193A (en) * | 1996-07-19 | 1999-03-02 | Hoffmann-La Roche Inc. | Use of N-(4-aryl-thiazol-2-yl)-sulfonamides |
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| DE1172258B (en) * | 1963-02-14 | 1964-06-18 | Basf Ag | Process for the continuous production of toluenesulfonic acid chlorides |
| US3686300A (en) * | 1969-03-14 | 1972-08-22 | Joachim Oten | Process for the preparation of p-toluenesulfochloride |
| CN1163264A (en) * | 1997-03-10 | 1997-10-29 | 刘国梁 | Process for producing p-toluenesulfonyl chloride |
| CN1405151A (en) * | 2002-11-04 | 2003-03-26 | 武汉大学 | Method for preparing sulfonyl chloro aromatics |
| CN1436773A (en) * | 2003-01-20 | 2003-08-20 | 浙江大学 | Synthesis process of tolylsulfonyl chloride |
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